CN102851019A - Preparation method of cationic viscoelastic surfactant fracturing fluid - Google Patents
Preparation method of cationic viscoelastic surfactant fracturing fluid Download PDFInfo
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- CN102851019A CN102851019A CN2012103881026A CN201210388102A CN102851019A CN 102851019 A CN102851019 A CN 102851019A CN 2012103881026 A CN2012103881026 A CN 2012103881026A CN 201210388102 A CN201210388102 A CN 201210388102A CN 102851019 A CN102851019 A CN 102851019A
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Abstract
The invention relates to a preparation method of a cationic viscoelastic surfactant fracturing fluid, which is characterized by comprising the following steps: dissolving 2-8g of cationic surfactant in 200mL of deionized water, heating to 40-60 DEG C, adding certain amounts of organic salt sodium styrene sulfonate and inorganic salt, evenly stirring for 90-240 minutes, naturally cooling to room temperature, and aging at room temperature for 12-48 hours, thereby obtaining the cationic viscoelastic surfactant fracturing fluid. The apparent viscosity of the cationic viscoelastic surfactant fracturing fluid is 100-400 mPa.s, the sedimentation rate is 0.02-0.4 mm/s, the gel breaking time for water is 50-200 minutes, and the gel breaking time for oil is 5-20 minutes; the apparent viscosity at the shear rate of 200s<-1> is 50-200 mPa.s; and the apparent viscosity at 80 DEG C is 30-100 mPa.s.
Description
Technical field
The present invention relates to the of the fracturing fluid preparation method of a kind of cationic viscoelastic surfactant, the cationic viscoelastic surfactant fracturing liquid of the present invention's preparation is applicable to the exploratory development of conventional and unconventional petroleum resources (coal-seam gas, shale gas and shale wet goods).
Background technology
The most normal fracturing liquid that uses is aqueous fracturing fluid both at home and abroad at present, and it is broadly divided into 3 types: natural phant fracturing fluid, Mierocrystalline cellulose fracturing liquid, synthetic polymer hydrofracturing fluid.These fracturing liquids have satisfied the site operation requirement basically, but because polymericular weight is large, and dispersing and dissolving is poor in water, and water-insoluble is relatively many, and its utilization ratio is lower, the scene can only remedy the poorly soluble dose losses of bringing to improve dosage.Thickening material and linking agent have been cross-linked to form the super large molecule in addition, water-soluble is poorer, and after pressure break finished, the super large molecule that quite a few water-insoluble (20%～60%) is arranged and thoroughly do not break glue resided in the formation fracture, zone permeability is descended, reduced the fracturing reform effect.And the row of returning of aqueous fracturing fluid leads extremely lowly, and formation contaminant is serious.
In recent years, viscoelastic surfactant fracturing liquid (VES) has high surface owing to it and unique rheological characteristics enjoys the Chinese scholars extensive concern, and carried out comparatively widely research to the of the fracturing fluid character of viscoelastic surfactant and in the application in pressure break, gravpack, acidifying, secondary oil recovery etc. field, and made some progress.It is serious that the traditional polymer fracturing liquid increases leak-off with pressure, and the VES fracturing liquid is insensitive to pressure.The traditional polymer fracturing liquid is easily degraded under stratum high-temperature simultaneously, destroys the fracturing liquid performance.In addition, fracturing liquid does not contain polymkeric substance, has significantly reduced the adsorptive capacity of residue on propping agent filling tape and fracture faces, forms the crack of high flow conductivity.The VES fracturing liquid is different from polymer fracturing fluid, and it can not stay filter cake without building capacity, and is therefore less to the stratum pollution level, improved negative skin coefficient, thereby increased Oil ﹠ Gas Productivity.Therefore all in all, the VES fracturing liquid has prepares the advantages such as easy, that construction is simple, consumption is few, frictional resistance is little, prop-carrying capacity is strong, the row of returning is easy, formation damage is little, the rear oil well production increasing of processing is remarkable, when especially at sea frac job is carried out in the oil field, can directly use the seawater preparing fracturing fluid, operation becomes simply, economy, efficient thereby make.
VES is a kind of surfactant soln system that can form under certain conditions flexibility claviform glues and the mutual winding reversible three-dimensional space net structure of formation and show special rheological property in the aqueous solution.That VES solution mainly is divided into is cationic, anionic, non-ionic type and amphoteric ion type etc.The VES solution of most study is cationic system at present, mix by a certain percentage the solution that forms by long chain alkyl ammonium salt and chain alkyl halogenation pyridine with halogenide, nitrate and organic salt (such as sodium salicylate, toluenesulfonate) etc., under quite low concentration, just has very high viscosity and significant elasticity, such as the mixed aqueous solution of cetyl trimethyl salamide solution, hexadecyl halogenation pyridine and sodium salicylate; The mixed system of 9-icosa alkene-methyl dihydroxy ethyl ammonium chloride and sodium salicylate etc.; The mixed system of dodecyl tributyl brometo de amonio and sodium lauryl sulphate, soltion viscosity is large to the degree that almost can't flow, and has simultaneously shear thinning behavior.Another kind of Novel ion tensio-active agent is twin (Shuangzi) tensio-active agent, contains simultaneously 2 hydrophobic long-chains, 2 hydrophilic radical ions and 1 bridged group in its molecule, can form viscoelastic solution when very low not adding other component and concentration.Nonionogenic tenside will (generally all greater than adding %) just have viscous-elastic behaviour in dense situation, thereby has restricted its widespread use.The anionic viscoelastic surfactant is relatively less in field use research.Yang Biao etc. have developed a kind of novel viscoelastic surfactant fracturing liquid (VES-SL), and this clean fracturing fluid has good temperature resistance thickening properties, and the highest temperature resistance ability is 120 ℃.Shop experiment shows that fracturing liquid is under the effect of diesel oil, local water, and broken gel is thorough, and low to the reservoir permeability injury, flow conductivity remains on more than 92 %.This fracturing liquid also has the characteristics that frictional resistance is low, the row of returning thorough, can place for a long time.Yin Zhong launches research to the high temperature resistant property of clean fracturing fluid, at laboratory synthetic surfactant GPP, make fracturing liquid can temperature resistance under the normal pressure more than 120 ℃ by adding NaCl and KCl, 120 ℃ of lower apparent viscosity have good applicability for being respectively 2510 mPas and 3415mPas.Jia Zhenfu develops a kind of novel gemini surfactant N, two octadecyl-the N of N-, N, N, N-tetrol ethyl-dibromo second two ammoniums (Gemini-OHAB), this system has good visco-elasticity, outstanding grittiness energy, dissolution in low temperature and temperature resistance stability, and temperature resistance can reach 125 ℃.And owing to introduced pure ethyl in the gemini surfactant, this New Fracturing Fluid system has solved the insoluble and high bio-toxicity of low temperature of traditional quaternary ammonium salt clean fracturing liquid system, has also overcome the low shortcoming of betaines clean fracturing liquid system heat-resisting property.The people such as Zhao Mengyun develop a kind of middle high temperature VES fracturing liquid tensio-active agent NTX2100, this fracturing fluid system is that NTX2100,0.3 % pH conditioning agent, 3.0 %KCl and the clear water of 4.0 % forms by massfraction, water-soluble good, spontaneous broken glue reaches 80 %.Fracturing fluid system temperature resistant capability with NTX2100 preparation reaches more than 110 ℃, can be used for vast in low hot-well pressing crack construction.Chen Kai has synthesized alkylamide quaternaries cation viscoelastic surfactant (being called for short EA222), and 3 %EA222+2 %KCl systems are at 80 ℃, and apparent viscosity reaches 86mPas under 105 s-1 condition, and this system can satisfy the requirement of outstanding grittiness.Lower, the broken glue of filtration rate is simple thoroughly during by the water saturated flow in low permeability core of salt, residue is few, breaking glue solution viscosity is low for system, the easy row of returning, and suitable rock temperature is below 90 ℃.A kind of nano particle of the application such as Huang carries out modification to cationic viscoelastic surfactant solution, and the result shows that VES solution temperature resistance and filtration reduction obviously improve; Ran etc. have investigated the impact of silicon dioxide colloid particle on cetyl trimethyl ammonium tosylate viscoelastic solution rheological, and the result shows that its viscoelastic solution zero-shear viscosity obviously increases, and at high temperature have good steady sticking ability.
The Schlumberger Dowell of foreign oil company develops a kind of novel non-polymer fracturing liquid, not only overcomes conventional fracturing liquid to the injury on stratum, and has the advantages such as dispersing and dissolving is fast, one-tenth glue speed is controlled, the admixture kind is few, dosing is very convenient.BJ SERVICES company has developed Aqua Clear and Elastra Frac viscoelastic surfactant fracturing fluid system, and temperature tolerance is good, reaches as high as 121 ℃.When ENI-Agip Spa carries out frac job in Adriatic Giovanna oil field, compare test at oil wells such as EMMAA6, EMMAA8 and Giovanna 6 with polymer fracturing fluid and clean fracturing fluid, find that clean fracturing fluid carries out the frac job oil well, not only formation damage greatly reduces, and oil well output is desirable, accomplishes the end in view.Dust Reno oil field compression fracture operation at Oklahoma, United States also draws same conclusion.Since 2000, domestic long celebrating oil field, Daqing oil field, Gas field philosophy were introduced the clean fracturing fluid of Schlumberger Dowell company, part well production increment successful.
The cationic viscoelastic surfactant fracturing liquid of report is by long chain alkyl ammonium salt and chain alkyl halogenation pyridine and halogenide at present, nitrate and organic salt are (such as sodium salicylate, toluenesulfonate) etc. mix by a certain percentage and form, cats product is higher than under 60 ℃ in temperature, visco-elasticity can reduce greatly, lose the Effective Suspension effect to propping agent, by cats product and organic salt Sodium styrene sulfonate and the cationic viscoelastic surfactant fracturing liquid of the compound preparation of inorganic salt to improve of the fracturing fluid temperature resistance, shear resistant and visco-elasticity yet there are no report both at home and abroad.
Summary of the invention
In view of this, purpose of the present invention is providing a kind of cationic viscoelastic surfactant of the fracturing fluid preparation method exactly.Adopt cats product and organic salt Sodium styrene sulfonate and the cationic viscoelastic surfactant fracturing liquid of the compound preparation of inorganic salt, by the of the fracturing fluid temperature resistance of adding raising viscoelastic surfactant, shear resistant and the visco-elasticity of organic salt Sodium styrene sulfonate and inorganic salt.
According to purpose of the present invention, the of the fracturing fluid preparation method of a kind of cationic viscoelastic surfactant has been proposed, its feature has following processing step:
2～8g cats product is dissolved in the 200mL deionized water, be warmed up to 40～60 ℃, then add quantitative organic salt Sodium styrene sulfonate and inorganic salt, uniform stirring 90～240 minutes, naturally cool to room temperature, ageing is 12～48 hours under room temperature, namely obtain cationic viscoelastic surfactant fracturing liquid, apparent viscosity is 100～400 mPa.s, settling velocity is 0.02～0.4mm/s, and the broken glue time of water is 50～200min, the broken glue time 5～20min of oil, apparent viscosity is 50～200 mPa.s under the shearing rate 200s-1, and 80 ℃ of apparent viscosity are 30～100 mPa.s.
Cats product used in the present invention is selected from cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, cetyltriethylammonium bromide, octadecyl triethyl brometo de amonio, palmityl trimethyl ammonium chloride and palmityl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide and dodecyl benzyl dimethyl ammonium chloride.
Inorganic salt used in the present invention are selected from KCl, KBr, NaCl, NaBr, NaNO
3And KNO
3
The mass ratio of cats product used in the present invention, organic salt Sodium styrene sulfonate and inorganic salt is 1～6:1～5:1～2.
Advantage of the present invention and effect are:
1) the of the fracturing fluid temperature resistance of reasonably combined raising cationic viscoelastic surfactants, shear resistant and the visco-elasticity by organic salt Sodium styrene sulfonate and inorganic salt.
2) have preparation easily, construction is simple, consumption is few, frictional resistance is little, prop-carrying capacity is strong, the row of returning easily, the advantage such as formation damage is little, the rear oil well production increasing of processing is remarkable, when especially at sea frac job is carried out in the oil field, can directly use the seawater preparing fracturing fluid, make operation become simply, economical, efficient.
3) compare with the conventional polymer fracturing liquid, the cationic viscoelastic surfactants fracturing liquid does not contain polymkeric substance, does not need to add linking agent, gel breaker and sterilant, can be broken glue behind crude oil, water or other stratum liquid dilutings.
The of the fracturing fluid temperature resistance of cationic viscoelastic surfactant of the present invention, shear resistant, take grittiness energy and broken colloidality can measuring method as follows.
The mensuration of viscoelastic surfactant fracturing liquid temperature resistance
Adopt the of the fracturing fluid apparent viscosity variation with temperature of viscoelastic surfactant situation under the NXS-11B type rotary viscosity design determining differing temps.
The mensuration of viscoelastic surfactant fracturing liquid shear resistant
The of the fracturing fluid apparent viscosity of viscoelastic surfactant is with the changing conditions of shearing rate under the employing NXS-11B type rotary viscosity design determining different shear rate.
The viscoelastic surfactant fracturing liquid is taken the mensuration of grittiness energy
A certain amount of viscoelastic surfactant fracturing liquid is joined in the long tool plug of the 10cm graduated cylinder; then the haydite or the granulated glass sphere that with diameter are 0.4～0.8cm are put into long tool plug graduated cylinder gently; measure haydite or granulated glass sphere and arrive the tool plug graduated cylinder used time of bottom; calculate the settling velocity of haydite or granulated glass sphere, settling velocity is calculated as follows:
In the formula: v-haydite or granulated glass sphere settling velocity, m/s;
L-haydite or granulated glass sphere settling height, m;
T-haydite or granulated glass sphere settling time, s.
The mensuration of viscoelastic surfactant fracturing liquid rubber-breaking performance
At room temperature the viscoelastic surfactant fracturing liquid is mixed by the volume ratio of 1:3 by the 5:1 volume ratio or with deionized water with hexanaphthene or gasoline, the glue phenomenon is broken in vibration evenly rear the observation, calculates the broken glue time, the apparent viscosity behind the broken glue of mensuration.
Four, embodiment
In order to understand better the present invention, further set forth content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
The 4g cetyl trimethylammonium bromide is dissolved in the 200mL deionized water, is warmed up to 50 ℃, then add 1.33g Sodium styrene sulfonate and 1g KNO
3Uniform stirring 200 minutes, naturally cool to room temperature, ageing is 48 hours under room temperature, namely obtains cationic viscoelastic surfactant fracturing liquid, apparent viscosity is 200 mPa.s, settling velocity is 0.3 mm/s, and the broken glue time of water is 80min, the broken glue time 7min of oil, apparent viscosity is 150 mPa.s under the shearing rate 200s-1, and 80 ℃ of apparent viscosity are 84mPa.s.
Embodiment 2:
The 6g cetyl trimethylammonium bromide is dissolved in the 200mL deionized water, be warmed up to 60 ℃, then add 2g Sodium styrene sulfonate and 1g KBr, uniform stirring 240 minutes, naturally cool to room temperature, ageing is 48 hours under room temperature, namely obtain cationic viscoelastic surfactant fracturing liquid, apparent viscosity is 300 mPa.s, settling velocity is 0.05mm/s, and the broken glue time of water is 120min, the broken glue time 15min of oil, apparent viscosity is 200 mPa.s under the shearing rate 200s-1, and 80 ℃ of apparent viscosity are 100 mPa.s.
Embodiment 3:
The 5g Cetyltrimethylammonium bromide is dissolved in the 200mL deionized water, is warmed up to 60 ℃, then add 4g Sodium styrene sulfonate and 1.5g NaNO
3Uniform stirring 240 minutes, naturally cool to room temperature, ageing is 48 hours under room temperature, namely obtains cationic viscoelastic surfactant fracturing liquid, apparent viscosity is 240 mPa.s, settling velocity is 0.08mm/s, and the broken glue time of water is 100min, the broken glue time 10min of oil, apparent viscosity is 150 mPa.s under the shearing rate 200s-1, and 80 ℃ of apparent viscosity are 90 mPa.s.
Embodiment 4:
3.5 g cetyltriethylammonium bromides are dissolved in the 200mL deionized water, be warmed up to 60 ℃, then add 2.5g Sodium styrene sulfonate and 1g NaBr, uniform stirring 240 minutes, naturally cool to room temperature, ageing is 48 hours under room temperature, namely obtain cationic viscoelastic surfactant fracturing liquid, apparent viscosity is 150mPa.s, settling velocity is 0.4mm/s, and the broken glue time of water is 70min, the broken glue time 6min of oil, apparent viscosity is 90 mPa.s under the shearing rate 200s-1, and 80 ℃ of apparent viscosity are 60 mPa.s.
Claims (5)
1. of the fracturing fluid preparation method of cationic viscoelastic surfactant is characterized in that having following processing step:
2～8g cats product is dissolved in the 200mL deionized water, be warmed up to 40～60 ℃, then add quantitative organic salt Sodium styrene sulfonate and inorganic salt, uniform stirring 90～240 minutes, naturally cool to room temperature, ageing is 12～48 hours under room temperature, namely obtains cationic viscoelastic surfactant fracturing liquid.
2. the of the fracturing fluid preparation method of a kind of cationic viscoelastic surfactant according to claim 1, it is characterized in that: described cats product is selected from cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, cetyltriethylammonium bromide, octadecyl triethyl brometo de amonio, palmityl trimethyl ammonium chloride and palmityl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide and dodecyl benzyl dimethyl ammonium chloride.
3. the of the fracturing fluid preparation method of a kind of cationic viscoelastic surfactant according to claim 1, it is characterized in that: described inorganic salt are selected from KCl, KBr, NaCl, NaBr, NaNO
3And KNO
3
4. the of the fracturing fluid preparation method of a kind of cationic viscoelastic surfactant according to claim 1, it is characterized in that: the mass ratio of described cats product, organic salt Sodium styrene sulfonate and inorganic salt is 1～6:1～5:1～2.
5. the of the fracturing fluid preparation method of a kind of cationic viscoelastic surfactant according to claim 1, it is characterized in that: described cationic viscoelastic surfactant fracturing liquid apparent viscosity is 100～400 mPa.s, settling velocity is 0.02～0.4mm/s, the broken glue time of water is 50～200min, the broken glue time 5～20min of oil, apparent viscosity is 50～200 mPa.s under the shearing rate 200s-1, and 80 ℃ of apparent viscosity are 30～100 mPa.s.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103173202A (en) * | 2013-03-04 | 2013-06-26 | 刘善祥 | High molecular surfactant fracturing fluid |
| CN103525392A (en) * | 2013-10-11 | 2014-01-22 | 北京国海能源技术研究院 | Degradable drag reducer for fracture and preparation method thereof |
| CN103897684A (en) * | 2014-03-20 | 2014-07-02 | 陕西省石油化工研究设计院 | Preparation method and application of unified clean fracturing fluid |
| CN105368438A (en) * | 2015-12-08 | 2016-03-02 | 辽宁石油化工大学 | Viscoelastic surfactant fracturing fluid and preparation method thereof |
| CN106000217A (en) * | 2016-05-24 | 2016-10-12 | 江南大学 | Viscoelastic system formed by functional Gemini surface active agent |
| CN106337676A (en) * | 2015-07-07 | 2017-01-18 | 中国石油天然气股份有限公司 | Method of fracturing coal-bed gas reservoir |
| CN106732165A (en) * | 2016-11-30 | 2017-05-31 | 江南大学 | A kind of false Gemini surface active agent and its construction method in water situ acid-base neutralization |
| CN106732166A (en) * | 2016-11-30 | 2017-05-31 | 江南大学 | A kind of cationic viscoelastic surfactant and its construction method |
| CN107760295A (en) * | 2017-11-08 | 2018-03-06 | 陕西友邦石油工程技术有限公司 | A kind of small molecule is recycled fracturing fluid and its application method |
| CN107828403A (en) * | 2017-11-28 | 2018-03-23 | 中国石油大学(北京) | Controllable surfactant clean fracturing fluid of a kind of microstructure and preparation method thereof |
| CN109705835A (en) * | 2018-12-29 | 2019-05-03 | 中国石油大学(华东) | A kind of halophilic viscoelastic surfactant clean fracturing fluid and preparation method thereof |
| CN110452679A (en) * | 2019-08-23 | 2019-11-15 | 四川洁能锐思石油技术有限公司 | A kind of shale gas fracturing fluid and preparation method thereof |
| CN111073626A (en) * | 2019-12-30 | 2020-04-28 | 陕西省石油化工研究设计院 | Clean fracturing fluid for low-permeability, high-temperature-resistant and high-pressure-resistant reservoir and preparation method thereof |
| CN112646559A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Sand carrying fluid with functions of improving flow resistance of thickened oil and stabilizing clay |
| CN116410729A (en) * | 2023-04-07 | 2023-07-11 | 西安石油大学 | Efficient low-damage clean fracturing fluid and preparation method thereof |
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| CN103525392A (en) * | 2013-10-11 | 2014-01-22 | 北京国海能源技术研究院 | Degradable drag reducer for fracture and preparation method thereof |
| CN103525392B (en) * | 2013-10-11 | 2016-03-23 | 北京国海能源技术研究院 | Degradable drag reducer for fracture and preparation method thereof |
| CN103897684A (en) * | 2014-03-20 | 2014-07-02 | 陕西省石油化工研究设计院 | Preparation method and application of unified clean fracturing fluid |
| CN103897684B (en) * | 2014-03-20 | 2016-06-29 | 陕西省石油化工研究设计院 | The preparation method of unified clean fracturing fluid and application |
| CN106337676B (en) * | 2015-07-07 | 2019-10-11 | 中国石油天然气股份有限公司 | A kind of fracturing process of coalbed methane reservoir |
| CN106337676A (en) * | 2015-07-07 | 2017-01-18 | 中国石油天然气股份有限公司 | Method of fracturing coal-bed gas reservoir |
| CN105368438A (en) * | 2015-12-08 | 2016-03-02 | 辽宁石油化工大学 | Viscoelastic surfactant fracturing fluid and preparation method thereof |
| CN106000217A (en) * | 2016-05-24 | 2016-10-12 | 江南大学 | Viscoelastic system formed by functional Gemini surface active agent |
| CN106732165A (en) * | 2016-11-30 | 2017-05-31 | 江南大学 | A kind of false Gemini surface active agent and its construction method in water situ acid-base neutralization |
| CN106732166A (en) * | 2016-11-30 | 2017-05-31 | 江南大学 | A kind of cationic viscoelastic surfactant and its construction method |
| CN107760295A (en) * | 2017-11-08 | 2018-03-06 | 陕西友邦石油工程技术有限公司 | A kind of small molecule is recycled fracturing fluid and its application method |
| CN107828403A (en) * | 2017-11-28 | 2018-03-23 | 中国石油大学(北京) | Controllable surfactant clean fracturing fluid of a kind of microstructure and preparation method thereof |
| CN109705835A (en) * | 2018-12-29 | 2019-05-03 | 中国石油大学(华东) | A kind of halophilic viscoelastic surfactant clean fracturing fluid and preparation method thereof |
| CN109705835B (en) * | 2018-12-29 | 2021-05-28 | 中国石油大学(华东) | High-salt-resistant viscoelastic surfactant clean fracturing fluid and preparation method thereof |
| CN110452679A (en) * | 2019-08-23 | 2019-11-15 | 四川洁能锐思石油技术有限公司 | A kind of shale gas fracturing fluid and preparation method thereof |
| CN112646559A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Sand carrying fluid with functions of improving flow resistance of thickened oil and stabilizing clay |
| CN111073626A (en) * | 2019-12-30 | 2020-04-28 | 陕西省石油化工研究设计院 | Clean fracturing fluid for low-permeability, high-temperature-resistant and high-pressure-resistant reservoir and preparation method thereof |
| CN116410729A (en) * | 2023-04-07 | 2023-07-11 | 西安石油大学 | Efficient low-damage clean fracturing fluid and preparation method thereof |
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